JP2001151885A - Hardening polyphenylene ether resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the surface nature of the electroless nickel/gold plate in the process for manufacturing the printed circuit boards without adverse effect on the excellent dielectric and mechanical properties of PPE resin. SOLUTION: The objective curable resin composition is prepared by using (a) a curable poly(phenylene ether) resin composition and (b) one or more kinds of peroxides selected from the group consisting of t-butyl cumyl peroxide, 2,5- dimethyl-2,5-(t-butyl peroxy)hexane, t-butyl-peroxy benzoate, n-butyl 4,4-bis(t- butylperoxy) valerate and 2,5-dimethyl-2,5-bis-(benzoylperox)hexane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a curable resin composition,
And a cured product obtained by curing the same. Further, the present invention provides a curable composite material comprising the resin composition and a substrate,
The present invention relates to a cured product thereof, a laminate comprising the cured product and a metal foil, and a metal foil with a resin. The resin composition of the present invention can be used for dielectric materials and insulating materials in the fields of the electronics industry, the space and aircraft industries, and the like.

[0002]

2. Description of the Related Art In recent years, there has been a remarkable trend toward miniaturization and high-density mounting methods in the field of electronic devices for communication, consumer use, industrial use, and the like, and accordingly, materials have become more excellent. Heat resistance, dimensional stability, electrical properties, and moldability are being demanded. For example, a conventional copper-clad laminate using a thermosetting resin such as phenol resin or epoxy resin has been used as a printed wiring board. Although these have various performances in a well-balanced manner, they have a drawback that electric characteristics, particularly, dielectric characteristics in a high frequency range are poor. As a new material for solving this problem, polyphenylene ether has recently attracted attention and is being applied to copper-clad laminates.

However, when a copper-clad laminate of a curable polyphenylene ether resin is used, the surface properties of electroless nickel / gold plating, which is widely used in the process of manufacturing a printed wiring board, are compared with those of an epoxy resin or the like. Some have pointed out that it is inferior.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has been made in the production process of a printed wiring board without impairing the excellent dielectric and mechanical properties of polyphenylene ether resin. An object of the present invention is to provide a curable polyphenylene ether-based resin composition having improved surface properties of electrolytic nickel / gold plating.

[0005]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found a novel resin composition that meets the object of the present invention, and have completed the present invention. Reached. The present invention is constituted by the following six inventions. A first aspect of the present invention is (a) a curable polyphenylene ether-based resin composition, and (b) t-butyl cumyl peroxide, 2,5-dimethyl-2,5 based on 100 parts by weight of the component (a). -Di (t-butylperoxy) hexane, t-butyl-peroxybenzoate, n-butyl 4,4-bis (t-butylperoxy) valerate, and 2,5-dimethyl-2,5-bis (benzoylperoxy) A curable resin composition comprising 0.1 to 10 parts by weight of one or more peroxides selected from the group consisting of hexane.

A second aspect of the present invention provides a cured resin composition obtained by curing the curable resin composition of the first aspect.
A third aspect of the present invention provides a curable composite material comprising the curable resin composition of the first invention and a substrate. A fourth aspect of the present invention provides a cured composite material obtained by curing the curable composite material of the third aspect. A fifth aspect of the present invention provides a laminate comprising the cured composite material of the fourth aspect and a metal foil. A sixth aspect of the present invention provides a resin-attached metal foil characterized in that a film of the curable resin composition of the first invention is formed on one side of the metal foil.

[0007] These inventions will be described in detail below. The curable polyphenylene ether-based resin composition used in the present invention is a composition containing a polyphenylene ether-based resin (including a modified product) as a component. Preferred examples of the above polyphenylene ether-based resin include:
Poly (2,6-dimethyl-1,4-phenylene ether) obtained by homopolymerization of 2,6-dimethylphenol,
Styrene graft polymer of poly (2,6-dimethyl-1,4-phenylene ether), copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, 2,6-dimethylphenol and 2-methyl-6- A polyfunctional polyphenylene ether resin obtained by polymerization in the presence of a copolymer of phenylphenol, 2,6-dimethylphenol and a polyfunctional phenol compound, for example, JP-A-63-301222, JP-A-1-297428
And copolymers containing the units of the general formulas (A) and (B) as disclosed in JP-A No. 10-260, 1988.

As for the molecular weight of the polyphenylene ether resin described above, the viscosity number ηsp / c measured with a 0.5 g / dl chloroform solution at 30 ° C. is 0.1 to 1.
Those in the range of 0 can be used favorably. Further, the polyphenylene ether-based resin referred to in the present invention also includes modified products. Examples of such modified products include polyphenylene ether resins containing unsaturated groups (Japanese Patent Application Laid-Open No. Sho 64-64).
-69628, JP-A-1-113425, JP-A-1
And the reaction products of polyphenylene ether resins with unsaturated carboxylic acids and / or acid anhydrides.

Next, as the resin to be blended in addition to the above-mentioned polyphenylene resin, any resin may be used as long as it does not impair the physical properties of the substrate as a material for a printed substrate, which is the object of the present invention. Specific examples of such a resin include a phenol resin, an epoxy resin, diallyl phthalate, divinylbenzene, a polyfunctional acryloyl compound, a polyfunctional methacryloyl compound, a polyfunctional maleimide, a polyfunctional methacryloyl compound, and a polyfunctional resin. Crosslinkable polymers such as maleimide, polyfunctional cyanate ester, polyfunctional isocyanate, unsaturated polyester, triallyl isocyanurate, triallyl cyanurate, polybutadiene, styrene-butadiene / styrene-butadiene-styrene, and various thermoplastic resins And various thermosetting resins. These are generally blended for the purpose of improving the physical properties of a substrate produced by laminating and molding a prepreg.

Preferred examples of the resin composition used in the present invention include polyphenylene ether and triallyl isocyanurate and / or triallyl cyanurate, polyphenylene ether and styrene butadiene block copolymer and triallyl isocyanurate and / or triallyl cyanate. Nylates, polyphenylene ethers containing unsaturated groups and triallyl isocyanurate and / or triallyl cyanurate, polyphenylene ethers containing unsaturated groups and triallyl isocyanurate and / or triallyl cyanurate and epoxy resins, polyphenylene ether resins and polyphenylene ether resins Reaction products with saturated carboxylic acids and / or acid anhydrides and triallyl isocyanurate and / or triallyl cyanurate Polyphenylene ether resin and an unsaturated carboxylic acid and / or reaction products of anhydrides and triallyl isocyanurate and / or triallyl cyanurate and an epoxy resin.
The amount of each component in these systems is selected according to the purpose.

The amount of the peroxide (b) used in the resin composition of the present invention is from 0.1 to 100 parts by weight of the component (a).
It is 1 to 10 parts by weight, preferably 0.1 to 8 parts by weight.
If the amount is less than 0.1 part by weight, the heat resistance of the cured resin is not sufficient. If the amount exceeds 10 parts by weight, the electric dielectric properties of the cured resin are reduced. In practicing the present invention, t-butyl cumyl peroxide or 2,5-dimethyl-
2,5-di (t-butylperoxy) hexane or t
-Butyl-peroxybenzoate or n-butyl-4,4-bis (t-butylperoxy) valerate or 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane are each used alone, Both can be mixed and used at an arbitrary ratio.

The resin composition of the present invention can be further used in the form of a filler or an additive in an amount that does not impair the original properties, for the purpose of imparting desired performance according to its use. Examples of the filler include carbon black, silica, alumina, barium titanate, talc, mica, glass beads, and glass hollow spheres. Examples of the additives include an antioxidant, an ultraviolet absorber, a heat stabilizer, an antistatic agent, a fluorescent agent, a plasticizer, a pigment, a dye, and a colorant. In order to further improve the flame retardancy, chlorine-based, bromine-based, phosphorus-based, silicon-based flame retardants, Sb2O3,
A flame retardant aid such as Sb2O5 may be used in combination.

Further, one or more kinds of other thermoplastic resins or thermosetting resins can be blended. Examples of the thermoplastic resin include polyethylene, polypropylene, polybutene, ethylene / propylene copolymer, polyolefins such as poly (4-methyl-pentene) and derivatives thereof, nylon 4, nylon 6, nylon 6.
6, polyamides such as nylon 6,10 and nylon 12 and derivatives thereof, polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene terephthalate / polyethylene glycol block copolymer and derivatives thereof, polyphenylene ether, modified polyphenylene Ether, polycarbonate, polyacetal, polysulfone, polyvinyl chloride and its copolymer, polyvinylidene chloride and its copolymer, polymethyl methacrylate, acrylic acid (or methacrylic acid) ester copolymer, polystyrene, acrylonitrile styrene Copolymers, polystyrenes such as acrylonitrile styrene butadiene copolymers and their copolymers, polyvinyl acetates, Vinyl formal, polyvinyl acetal, polyvinyl butyral, ethylene vinyl acetate copolymer and its hydrolyzate, polyvinyl alcohol, styrene butadiene block copolymer, rubber such as polybutadiene, polyisoprene, polymethoxyethylene, polyethoxy Polyvinyl ethers such as ethylene, polyacrylamide, polyphosphazenes,
Examples thereof include liquid crystal polymers such as polyether sulfone, polyether ketone, polyether imide, polyphenylene sulfide, polyamide imide, thermoplastic polyimide, and aromatic polyester, and side chain type liquid crystal polymers having a liquid crystal component in a side chain. Examples of the thermosetting resin include an epoxy resin and a polyimide precursor.

The second cured resin composition of the present invention is obtained by curing the curable resin composition described above. The method of curing is arbitrary, and a method using heat, light, an electron beam, or the like can be employed. When curing by heating, the temperature varies depending on the peroxide.
The temperature is selected in the range of 0 to 300 ° C, more preferably 100 to 250 ° C. The time is about 1 minute to 10 hours, more preferably 1 minute to 5 hours.

The resin composition of the obtained cured polyphenylene ether resin composition can be analyzed by a method such as infrared absorption spectroscopy, high-resolution solid nuclear magnetic resonance spectroscopy, and pyrolysis gas chromatography. Further, this curable polyphenylene ether-based resin composition contains a metal foil and / or
Alternatively, it can be used by being bonded to a metal plate.

Next, the third and fourth curable composite materials of the present invention and their cured products will be described. The third curable composite material of the present invention is characterized by comprising the curable resin composition according to the first present invention and a substrate. As the base material of the component (c), various glass cloths such as a roving cloth, cloth, chopped mat, and surfacing mat, asbestos cloth, metal fiber cloth and other synthetic or natural inorganic fiber cloths; Woven or non-woven fabric obtained from liquid crystal fiber such as aromatic polyester fiber or polybenzozar fiber; woven or non-woven fabric obtained from synthetic fiber such as polyvinyl alcohol fiber, polyester fiber, acrylic fiber, polytetrafluoroethylene fiber; cotton cloth; Natural fiber cloth such as linen cloth and felt; carbon fiber cloth; natural cellulosic cloth such as kraft paper, cotton paper, paper-glass mixed fiber paper
Alternatively, two or more kinds are used in combination.

Component (c) accounts for 5 to 90 parts by weight, preferably 10 to 80 parts by weight, and more preferably 20 to 70 parts by weight, based on 100 parts by weight of the curable composite material.
Parts by weight. When the amount of the component (c) is less than 5 parts by weight, the dimensional stability and strength of the composite material after curing are insufficient.
On the other hand, when the amount of the base material is more than 90 parts by weight, the dielectric properties of the composite material are inferior, which is not preferable. In the composite material of the present invention, if necessary, a coupling agent can be used for the purpose of improving the adhesion at the interface between the resin and the base material. As the coupling agent, general ones such as a silane coupling agent, a titanate coupling agent, an aluminum-based coupling agent, and a zircoaluminate coupling agent can be used.

The method of combining the curable resin composition of the present invention with a substrate is not particularly limited as long as it is under conditions that cause a significant decomposition reaction of the peroxide. And a method of uniformly dissolving or dispersing the substance and, if necessary, other components in a halogen-based, aromatic-based, ketone-based solvent, or a mixed solvent thereof, impregnating the substrate, and then drying. The impregnation is performed by dipping (dipping), coating, or the like. The impregnation can be repeated multiple times as necessary, and in this case, the impregnation can be repeated using multiple solutions having different compositions and concentrations to finally adjust the desired resin composition and resin amount It is.

The fourth cured composite material of the present invention is obtained by curing the curable composite material thus obtained by a method such as heating. The manufacturing method is not particularly limited.For example, a plurality of the curable composite materials are stacked, and the respective layers are adhered to each other under heat and pressure, and simultaneously heat-cured to obtain a cured composite material having a desired thickness. Can be. Further, it is also possible to obtain a cured composite material having a new layer configuration by combining the cured composite material once cured by adhesion and the curable composite material. Lamination molding and curing are usually performed simultaneously using a hot press or the like, but both may be performed independently. That is, the uncured or semi-cured composite material obtained by lamination molding in advance can be cured by heat treatment or another method.

The molding and curing are performed at a temperature of 80 to 300 ° C.
The reaction can be performed at a pressure of 0.1 to 500 kg / cm2 for a time of 1 minute to 10 hours, more preferably at a temperature of 100 to 250 ° C, a pressure of 1 to 100 kg / cm2, and a time of 1 minute to 5 hours. The fifth laminate of the present invention will be described. The laminate of the present invention is composed of the cured composite material described above as the fourth of the present invention and a metal foil. Examples of the metal foil used here include a copper foil and an aluminum foil. Although the thickness is not particularly limited, it is 5 to 200 μm, more preferably 5 to 105 μm.
m.

The method for producing the laminate of the present invention includes:
For example, a method of laminating the curable composite material described above as the third of the present invention with a metal foil and / or a metal plate in a layer structure according to the purpose, bonding the respective layers under heat and pressure, and simultaneously thermosetting. Can be mentioned. In the laminate of the present invention, the curable composite material and the metal foil are laminated in an arbitrary layer configuration. The metal foil can be used as both a surface layer and an intermediate layer.

In addition to the above, lamination and curing can be repeated a plurality of times to form a multilayer. An adhesive can be used for bonding the metal foil. Epoxy,
Acrylic-based, phenol-based, cyanoacrylate-based and the like can be mentioned, but not particularly limited thereto. The lamination and curing can be performed under the same conditions as in the fourth case of the present invention. Lastly, the sixth embodiment of the present invention will be described.

The copper foil with resin of the present invention comprises the above-mentioned curable resin composition and metal foil as the first of the present invention. Examples of the metal foil used here include a copper foil and an aluminum foil. Although the thickness is not particularly limited, it is 5 to 200 μm, more preferably 5 to 200 μm.
１０５105 μm. The method for producing the resin-coated copper foil of the present invention is not particularly limited as long as it is not a condition that causes a significant decomposition reaction of the peroxide. For example, the component (a) and the peroxide and, if necessary, The other components may be uniformly dissolved or dispersed in a halogen-based, aromatic-based, ketone-based solvent or the like or a mixed solvent thereof, and may be applied to a metal foil, followed by drying or melting and molding. .

The application can be repeated a plurality of times, if necessary. In this case, the application is repeated using a plurality of solutions having different compositions and concentrations to finally adjust the desired resin composition and resin amount. It is also possible.

[0025]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, specific examples of the present invention will be described with reference to embodiments. In the following examples, the following were used as each component. Peroxide: t-butyl cumyl peroxide (perbutyl C) 2,5-dimethyl-2,5-di (t-butyl peroxy) hexane (perhexa 25B) 2,5-dimethyl-2,5-bis (benzoyl peroxy) ) Hexane (Perhexa 25Z) (both manufactured by NOF Corporation) Flame retardant: decabromodiphenylethane (Asahi Glass Co., Ltd.)
SAYTEX-8010) Flame-retardant auxiliary agent: Sb2O3 (NATSU PAPER CO., LTD.
X-M) Glass cloth: E glass, weight 71g / m2

[0026]

Reference Example 1 Poly (2,500) having a viscosity number ηsp / c of 0.53 as measured with a 0.5 g / dl chloroform solution at 30 ° C.
6-dimethyl-1,4-phenylene ether), 1.5 parts by weight of maleic anhydride, and 2,5-
After dry-blending 1.0 part by weight of dimethyl-2,5-di (t-butylperoxy) hexane (Perhexa 25B manufactured by NOF Corporation) at room temperature, the cylinder temperature was 30.
Extrusion was performed by a twin screw extruder under the conditions of 0 ° C. and a screw rotation speed of 230 rpm. Viscosity number ηsp / c of reaction product measured in chloroform solution of 0.5 g / dl at 30 ° C.
Was 0.58. This reaction product is designated as A.

[0027]

REFERENCE EXAMPLE 2 Viscosity number η measured by the same method as in Reference example 1.
poly (2,6-dimethyl-1,4 having an sp / c of 0.40
After dry blending 100 parts by weight of (phenylene ether) and 1.5 parts by weight of maleic anhydride at room temperature, the mixture was extruded with a twin screw extruder at a cylinder temperature of 300 ° C. and a screw rotation speed of 230 rpm. 30 ° C, 0.5g
The viscosity number ηsp / c of the reaction product measured with a chloroform solution of / dl was 0.43. This reaction product is
And

[0028]

Example 1 <Copper foil with resin> 66 parts by weight of polymer A,
30 parts by weight of triallyl isocyanurate, 3 parts by weight of t-butylcumyl peroxide, 20 parts by weight of a flame retardant, and 4 parts by weight of a flame retardant auxiliary are mixed with toluene as a solvent, and the
It was applied to an 8 μm electrolytic copper foil and dried to obtain a resin-coated copper foil.
The thickness of the resin part was 60 μm.

0.8 mm thick glass cloth reinforced thermosetting polyphenylene ether resin laminate (Risho Kogyo Co., Ltd.)
180 g of the above resin-coated copper foil on both surfaces of CS3376A).
Bonding and curing were performed by heating and pressing at a pressure of 30 kg / cm 2 at 2 ° C. for 2 hours to form a double-sided copper-clad laminate. The double-sided copper-clad laminate was selectively etched by a photographic method to form a conductive circuit pattern. Next, electroless nickel / gold plating was performed using a chemical solution of Okuno Pharmaceutical Co., Ltd. The plating conditions are as shown in Table 1. The surface properties of the obtained nickel / gold plating were uniform.

[0030]

[Table 1]

[0031]

Comparative Example 1 The same operation as in Example 1 was repeated except that dicumyl peroxide (Parkmill D manufactured by Nippon Oil & Fats Co., Ltd.) was used as the peroxide, and the plating surface properties were confirmed in the same manner. The resulting plating had a step having a portion where nickel deposition was small at the end of the pattern.

[0032]

Example 2 Laminate 66 parts by weight of polymer B, 37 parts by weight of triallyl isocyanurate, 2,5-dimethyl-
3 parts by weight of 2,5-di (t-butylperoxy) hexane, 20 parts by weight of a flame retardant, and 4 parts by weight of a flame retardant aid were mixed with toluene as a solvent, and a glass cloth (E glass, basis weight 71) was mixed.
g / m2) and dried to obtain a curable composite material. The resin amount of this curable composite material was 56% by weight. 18 μm thick electrolytic copper foil, 8 curable composite materials, thickness 1
8 μm electrolytic copper foils were laminated in this order and bonded and cured by heating and pressing at 180 ° C. for 2 hours at a pressure of 30 kg / cm 2 to form a double-sided copper-clad laminate having a thickness of 0.8 mm. The double-sided copper-clad laminate was selectively etched by a photographic method to form a conductive circuit pattern.

Next, the same electroless nickel /
Gold plating was performed. The surface properties of the obtained nickel / gold plating were uniform. Using the double-sided copper-clad laminate, a dielectric measurement sample specified in JIS C 6481 was prepared by selective etching. The dielectric constant and the dielectric loss tangent measured by the automatic equilibrium bridge method were 3.5 and 0.002, respectively.

[0034]

Comparative Example 2 t-hexyl peroxyisopropyl monocarbonate (perhexyl I) was used as a peroxide.
The same operation as in Example 2 was repeated except that Nippon Oil & Fats Co., Ltd. was used, and the plating surface properties were similarly confirmed. The resulting plating had a step having a portion where nickel deposition was small at the end of the pattern. Using the double-sided copper-clad laminate, a dielectric measurement sample specified in JIS C 6481 was prepared by selective etching. The dielectric constant and the dielectric loss tangent measured by the automatic equilibrium bridge method were 3.6 and 0.002, respectively.

[0035]

Example 3 <Resin sheet> 66 parts by weight of polymer B, 30 parts by weight of triallyl isocyanurate, 3 parts by weight of 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, 20 parts by weight of flame retardant, flame retardant 4 parts by weight of the auxiliary agent was mixed with toluene as a solvent, applied to a polyester film having a thickness of 50 μm, dried and peeled to obtain a resin sheet. The thickness of the resin sheet was 80 μm.

An electrolytic copper foil having a thickness of 18 μm, 10 sheets of the above-mentioned resin sheet, and an electrolytic copper foil having a thickness of 18 μm are stacked in this order.
The film was adhered and cured by heating and pressing at a pressure of 30 kg / cm 2 at 2 ° C. for 2 hours to form a double-sided copper-clad laminate having a thickness of 0.8 mm. The double-sided copper-clad laminate was selectively etched by a photographic method to form a conductive circuit pattern. Next, the same electroless nickel / gold plating as in Example 1 was performed.
The surface properties of the obtained nickel / gold plating were uniform.
Using the above double-sided copper-clad laminate, J
A dielectric measurement sample specified in IS C6481 was prepared. The dielectric constant and the dielectric loss tangent measured by the automatic equilibrium bridge method were 3.4 and 0.003, respectively.

[0037]

Comparative Example 3 t-butyl peroxy peroxide
2-ethylhexyl monocarbonate (Perbutyl E
The same operation as in Example 3 was repeated except that Nippon Oil & Fats Co., Ltd. was used, and the plating surface properties were similarly confirmed. The resulting plating had a step having a portion where nickel deposition was small at the end of the pattern. Using the double-sided copper-clad laminate, JIS C 6481 is selectively etched.
A dielectric measurement sample as specified in was prepared. The dielectric constant and the dielectric loss tangent measured by the automatic equilibrium bridge method were 3.5 and 0.002, respectively.

[0038]

According to the present invention, the curable resin composition of the present invention can be used as compared with the curable polyphenylene ether-based resin composition to date.
The surface properties of the gold plating are remarkably improved. In addition, the polyphenylene ether-based resin maintains excellent electrical insulation and dielectric properties. Therefore, the material of the present invention is
It can be used as a dielectric material, an insulating material and the like in the field of the electronic industry and the like.

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Claims (6)

[Claims] Claims 1. Based on (a) a curable polyphenylene ether-based resin composition and 100 parts by weight of component (a),
(B) t-butyl cumyl peroxide, 2,5-
Dimethyl-2,5-di (t-butylperoxy) hexane, t-butyl-peroxybenzoate, n-butyl 4,4-bis (t-butylperoxy) valerate, and 2,5-dimethyl-2,5- A curable resin composition comprising 0.1 to 10 parts by weight of one or more peroxides selected from the group consisting of bis (benzoyl peroxy) hexane. 2. A cured resin composition obtained by curing the curable resin composition according to claim 1. 3. A curable composite material comprising the curable resin composition according to claim 1 and (c) a base material, the base material comprising 5 to 90 parts by weight based on 100 parts by weight of the curable composite material. A curable composite material comprising: 4. A cured composite material obtained by curing the curable composite material according to claim 3. 5. A laminate comprising the cured composite material according to claim 4 and a metal foil. 6. A metal foil with resin, wherein the film of the curable resin composition according to claim 1 is formed on one surface of the metal foil.